CN104910399A

CN104910399A - Film, dope composition and manufacturing method thereof, and solution film-forming method

Info

Publication number: CN104910399A
Application number: CN201510088926.5A
Authority: CN
Inventors: 继枝爱; 池山昭弘; 鹫谷公人
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2014-03-11
Filing date: 2015-02-26
Publication date: 2015-09-16
Anticipated expiration: 2035-02-26
Also published as: KR20150106336A; TW201534641A; KR102364918B1; TWI659052B; JP6016252B2; CN104910399B; JP2015187251A

Abstract

The invention provides a film capable of reducing attachment during laminating, a dope composition and manufacturing method for manufacturing the film, and solution film-forming method for manufacturing the film. Protrusions (15), having particles, with a height over 30nm is formed on a film surface (10a) formed by polymer. The density of the protrusions (15) with a height over 30nm falls into a scope of 104/mm2 to 106/mm2. The protrusions (15) prevent partial direct contact between two opposite film surface (10a), thereby reducing attachment during laminating.

Description

Film, dope composition and manufacture method thereof and solution film-forming method

Technical field

The present invention relates to a kind of film, for the manufacture of the dope composition of this film and the solution film-forming method of manufacture method and manufacture film thereof.

Background technology

Polymeric film (hereinafter referred to as film) is widely utilized as the blooming such as protective membrane, phase retardation film, antireflection film, transparent and electrically conductive film of Polarizer.

Film, generally with microscler manufacture, as manufacture method, has solution film-forming method.Solution film-forming method is such as following method: by curtain coating mould, the solution (hereinafter referred to as dope (dope)) making polymkeric substance be dissolved in solvent forms banded casting films in the successively curtain coating of supporting mass, and carries out drying after stripping from supporting mass.Microscler film rolling is taken at core and preserves with web-like.

If batch microscler film, then lap attaches sometimes each other.As the countermeasure preventing from attaching, described in Japanese Patent Publication 2006-028251 publication, there is following film: add particulate, the quantity of the projection with more than 2 times height of the average rising height being set as 2 ~ 20nm is located at 1.0 × 10 of total projection quantity ^-6above 1.0 × 10 ^-2in following scope.

But if batch the film of Japanese Patent Publication 2006-028251 publication, then in fact lap can attach with certain probability each other.Especially, when batching microscler film, contact surface pressure puts between the lap of film, and therefore the lap of film attaches each other with higher probability.Further, if manufacture film compared with unfertile land or longer manufacture film or manufacture the lower film of Young's modulus, then attach with higher probability.So, put on the reasons such as the surface of film because of excessive pressure and cause overlapping film to attach each other, this phenomenon is also called adhesion (blocking).Further, due to this attaching, the film rolling coiling into web-like produces the depression being circumferentially referred to as " recess ", and produce wrinkle etc. on the film batched.

Summary of the invention

Therefore, the object of the present invention is to provide a kind of overlapping time attaching is reduced film, for the manufacture of the dope composition of this film and the solution film-forming method of manufacture method and manufacture film thereof.

Thin film of the present invention is standby: pellicular front, by polymer formation; And projection, to be formed on this pellicular front and to be highly more than 30nm.Projection comprises particulate.Every 1mm on pellicular front ²in area, with 10 ⁴individual above 10 ⁶individual following scope is formed with projection.

Polymkeric substance is preferably cellulose acylate.

Preferably every 1mm on pellicular front ²in area, with 10 ⁴individual above 10 ⁶individual following scope be formed pellicular front saponification process after projection.

Preferably the described pellicular front be adhered to by polarizing coating after saponification process uses.

Particulate is preferably silicon-dioxide.

Dope composition of the present invention possesses: polymkeric substance; Solvent, dissolves this polymkeric substance; And particulate, disperse with the state of offspring.Aggregate particle size is that the particulate of more than 0.7 μm is at least 30% relative to particulate sum containing proportional.

The manufacture method of dope composition of the present invention possesses raw material dope preparation process (step A), mixture preparation process (step B), microparticulate step (step C) and mixing step (D step).In step A, polymkeric substance and solvent are mixed, and at least one by heating and in stirring, described polymer dissolution is made raw material dope in described solvent.In step B, obtain liquid mixture by carrying out mixing with above-mentioned polymkeric substance and the congruent polymkeric substance of above-mentioned solvent phase and solvent and particulate and stir.In step C, particulate is disperseed as offspring in the mixture, thus obtains particle dispersion liquid.In particle dispersion liquid, the particulate of the aggregate particle size of more than 0.7 μm is at least 30% relative to particulate sum containing proportional.In D step, raw material dope and particle dispersion liquid are carried out mixing to obtain dope composition.

In step C, preferably by mixture being applied to ultrasonic wave or making particulate disperse as offspring in the mixture by use ball mill.

Solution film-forming method of the present invention possesses above-mentioned step A, above-mentioned step B, above-mentioned step C, above-mentioned D step, casting films forming step (E step) and strips drying step (F step).In E step, form casting films by the dope composition that spues continuously on the supporting mass be continuously traveling from curtain coating mould at supporting mass.In F step, obtain film by peeling casting films from supporting mass and carrying out drying.

According to the present invention, the attaching each other of the lap of film can be reduced.Therefore, the generation of the depression being circumferentially referred to as recess in film rolling and the wrinkle on the film batched etc. can be suppressed.

Accompanying drawing explanation

Fig. 1 is the sectional view of the summary of the film representing one embodiment of the present invention.

Fig. 2 is the amplification view near the pellicular front of the film of Fig. 1.

Fig. 3 is the sectional view of the summary representing the Polarizer utilizing the film of Fig. 1 to make.

Fig. 4 is the amplification profile schematic diagram of the part that the Polarizer of the part that overlaps each other of the film of Fig. 1 and Fig. 3 overlaps each other.

Fig. 5 is the explanatory view of the summary representing solution film-forming equipment.

Fig. 6 be represent aggregate particle size be more than 0.7 μm particulate relative to total particle number containing proportional and be highly more than 30nm projection density between the explanatory view of dependency.

Fig. 7 is the afm image relevant with the film manufactured in experiment 1-D.

Fig. 8 is the afm image for Fig. 7, using the example of the brightness corresponding with rising height 10nm as the image after threshold value carries out binary conversion treatment.

Fig. 9 is the afm image for Fig. 7, using the example of the brightness corresponding with rising height 30nm as the image after threshold value carries out binary conversion treatment.

Figure 10 represents to be highly the explanatory view of the dependency between the density of projection of more than 10nm and the ratio of the area of attachment of film.

Figure 11 represents to be highly the explanatory view of the dependency between the density of projection of more than 30nm and the ratio of the area of attachment of film.

Figure 12 represents to be highly the explanatory view of the dependency between the density of projection of more than 40nm and the ratio of the area of attachment of film.

Figure 13 represents to be highly the explanatory view of the dependency between the density of projection of more than 50nm and the ratio of the area of attachment of film.

Figure 14 represents rising height and the projection explanatory view to the dependency reduced between the contribution rate that attaches.

Figure 15 represents that aggregate particle size is that the particulate of more than 0.7 μm is relative to the explanatory view containing the dependency between the proportional and ratio of area of attachment of total particle number.

Embodiment

Be described with reference to the film 10 involved by figure 1 pair of embodiments of the present invention.Film 10 shown in Fig. 1 possesses main film body 12 and is configured at the top layer 13 in two faces of main film body 12.Although the border between main film body 12 and top layer 13 cannot be observed, in FIG, illustrate their border for convenience of explanation.

Main film body 12 is made up of cellulose acylate and additive.A pair top layer 13 is made up of identical composition, and specifically, any top layer 13 is formed by cellulose acylate, particulate 14 and additive, and its ratio is also identical.Additive is the delay inhibitor etc. of the delay of softening agent, UV light absorber and control film 10.Also additive can not be comprised in main film body 12 and a pair top layer 13.The surface of particulate 14 is coated by hydrophobic group institute, is the silicon-dioxide (silicon dioxide, the SiO that present offspring form ₂).In addition, together can use with silicon-dioxide in particulate 14 or replace silicon-dioxide and use titanium dioxide, aluminum oxide, zirconium white, calcium carbonate, talcum, clay, burn till kaolin, burn till Calucium Silicate powder, the particulate of calcium silicate hydrate, pure aluminium silicate, Magnesium Silicate q-agent, calcium phosphate etc.The detailed content of particulate 14 is by aftermentioned.

The cellulose acylate of main film body 12 is cellulosetri-acetate (Triacetyl Cellulose, TAC), and the cellulose acylate on top layer 13 is set to TAC.But each cellulose acylate on main film body 12 and top layer 13 is not limited thereto.Such as, also the cellulose acylate of main film body 12 can be set to Cellulose diacetate (Diacetyl Cellulose, DAC), the cellulose acylate on top layer 13 is set to TAC.Further, in the present embodiment, although each component of polymer on main film body 12 and top layer 13 is all set to cellulose acylate, as long as the polymkeric substance of film can be made by solution film-forming method.As other polymkeric substance, such as, there are cyclic polyolefin, vinylformic acid, polyethylene terephthalate (Polyethylene Terephthalate, PET) etc.

When forming two top layers 13 by identical composition, the ratio of composition can be mutually different.Further, can be the form only having a top layer in two top layers 13 to comprise particulate.Further, can be set to the single layer structure be made up of main film body 12, and not arrange two top layers 13, also can be the form that this main film body 12 is made up of cellulose acylate, additive and particulate 14.

The thickness T10 of film 10 is set to 60 μm, and the thickness T12 of main film body 12 is set to 54 μm, and the thickness T13 on top layer 13 is set to 3 μ n.But each thickness is not limited to this, as long as thickness T10 is more than 10 μm in the scope of less than 80 μm, thickness T12 is more than 8 μm in the scope of less than 75 μm, and thickness T13 is more than 1 μm in the scope of less than 10 μm.When thickness T10 more than 15 μm in the scope of less than 60 μm time, the effect reducing lap attaching each other when batching film 10 of the present invention is especially large.Thickness T10, T12, T13 can by calculating, and the concentration according to each solid substance of aftermentioned 1st dope 41 (with reference to figure 5) and the 2nd dope 42 (with reference to figure 5) is obtained with the amount flowing to curtain coating mould 65 (with reference to figure 5).

Further, when film 10 are Young's modulus is the low elastic modulus film of below 3.0GPa, the effect reducing film 10 attaching is each other larger too.At this, made the sample sections of 2cm × 15cm by film 10, and tension test is carried out to this sample sections, measure the Young's modulus of film 10 thus.The Strograph that tension test such as uses Toyo Seiki Seisaku-Sho Ltd. to manufacture carries out.The condition of tension test be hold sample sections two chucks between distance be 10cm, and the speed of pinblock is 200mm/ minute.

The pellicular front 10a that a part for particulate 14 in film 10 is set to from being formed by the TAC as component of polymer gives prominence to more than certain altitude, and wherein each all plays the effect of projection 15.Such as, as shown in Figure 2, it is the projection 15a of H15a that particulate 14a forms the height given prominence to from pellicular front 10a, and particulate 14b forms the projection 15b that this height is H15b.At this, be defined as pellicular front 10a from the height H [unit: nm] that pellicular front 10a is outstanding and distance between the summit of part of exposing from pellicular front 10a.In addition, Fig. 1,2 and Fig. 4 in, for convenience of explanation, show the projection that only formed by particulate 14 as projection 15, but the form of projection 15 is not limited to this.Projection 15 also for any form formed for basic point with particulate 14, such as, can be formed by the material of composite additive and cellulose acylate in particulate 14.When projection 15 is only formed by particulate 14, the summit of decision height H becomes the summit of particulate 14.When projection 15 is formed by the material of composite additive and cellulose acylate in particulate 14, the summit of decision height H becomes the summit farthest away from pellicular front 10a in the summit of the summit of particulate, the summit of additive, cellulose acylate.

Multiple projection 15 is set on pellicular front 10a by particulate 14, is formed small concavo-convex thus on pellicular front 10a, give certain roughness to pellicular front 10a.Concavo-convex by this, also mutually can not attach even if film 10 overlaps each other, film 10 slip each other can be guaranteed, thus show certain resistance to marring.So, particulate 14 plays the effect of so-called delustering agent.

When the height H of projection 15 is more than 30nm, compared with the situation being less than 30nm with the height H of projection 15, reduce film 10 attaching each other or improve the effect of sliding larger.Along with projection 15 uprises, reduce the effect attaching or improve sliding and increase, when the height H of projection 15 is more than 40nm, the effect reducing film 10 attaching each other or improve sliding increases further.Further, when the height H of projection 15 is below 100nm, with height H higher than 100nm situation compared with, the mist degree of film 10 is lower, therefore preferably.

By the every 1mm at pellicular front 10a ²the height of interior existence is that the number of the projection 15 of more than H is set to projection density D (H) [unit: individual/mm ²].Be highly that the projection density D (30) of more than 30nm is 10 ⁴individual/mm ²above 10 ⁶individual/mm ²in following scope.When the projection density D (30) highly for more than 30nm is 10 ⁴individual/mm ²time above, be less than 10 with projection density D (30) ⁴individual/mm ²situation compare, reduce the effect that attaches and give the effect of sliding larger.Along with the increase of projection density D (30), reduce the effect attached and the effect of giving sliding increase, when projection density D (30) is 2 × 10 ⁴individual/mm ²time above, the effect reducing effect and the imparting sliding attached increases further.Further, when projection density D (30) is 10 ⁶individual/mm ²time following, be greater than 10 with projection density D (30) ⁶individual/mm ²situation compare, the mist degree of film 10 is suppressed lower.When projection density D (30) is 5 × 10 ⁵individual/mm ²time following, the mist degree of film 10 is suppressed lower.In addition, about projection density D (40), the scope that the effect that minimizing attaches is larger with the effect of giving sliding is also identical with projection density D (30) with the scope suppressing lower by mist degree.

When the protective membrane using film 10 as Polarizer, saponification process is carried out to film 10.As shown in Figure 3, Polarizer 20 possesses polarizing coating 17 and a pair film 10, and film 10 is configured at each face of polarizing coating 17.Saponification process is carried out with the bonding force of polarizing coating 17 to improve.The pellicular front 10a of the pellicular front 10a opposite side bonding with polarizing coating 17 of film 10 becomes the surperficial 20a of Polarizer 20.In addition, saponification process is carried out usually on two pellicular front 10a of film 10, is also carry out two pellicular front 10a in present embodiment.

The saponification process of film 10 can be any condition, in the present embodiment, have saponifying process, the 1st matting, in and operation, the 2nd matting and drying process.In saponifying process, impregnated thin film 10 in alkali aqueous solution and make pellicular front 10a saponification.As alkali, such as, can use potassium hydroxide (KOH).In the 1st matting, clean the film 10 through saponifying process.Cleaning is such as carried out with pure water.In and in operation, using acid or aqueous acid as neutralizer, make to neutralize through the film 10 of the 1st matting with this neutralizer.In the 2nd matting, such as, clean in warp and the film 10 of operation with pure water.In drying process, drying is carried out to the film 10 through the 2nd matting.

Saponification process has saponification (saponification hereinafter referred to as the stronger) process of stronger condition and saponification (saponification hereinafter referred to as the more weak) process of comparatively slow condition, can be wherein any one.Each process conditions of stronger saponification process is as follows.In saponifying process, the KOH aqueous solution of concentration in the scope of more than 1.5mol/L below 5.0mol/L is used as alkali aqueous solution, the temperature of this KOH aqueous solution more than 45 DEG C in the scope of less than 60 DEG C, for the dipping time of the film 10 of this KOH aqueous solution more than 30 seconds in the scope of less than 130 seconds.In the 1st matting, clean with pure water, scavenging period is more than 10 seconds in the scope of less than 20 seconds.In and operation in, by the aqueous sulfuric acid (H of concentration in the scope of more than 0.05mol/L below 0.4mol/L ₂sO ₄aq) as neutralizer, this H ₂sO ₄the temperature of aq more than 20 DEG C in the scope of less than 30 DEG C, in and the time more than 10 seconds in the scope of less than 30 seconds.In the 2nd matting, clean with pure water, scavenging period is more than 100 seconds in the scope of less than 130 seconds.In drying process, carry out drying by the time of being placed more than 40 seconds less than 100 seconds by film 10 under the temperature environment in the scope of less than 130 DEG C more than 100 DEG C.

1st example (hereinafter referred to as the 1st Saponification Conditions) of stronger saponification treatment condition is as follows.

Saponifying process: flooded for 120 seconds in the KOH aqueous solution (KOH concentration is 2.0mol/L, and temperature is 55 DEG C)

1st matting: cleaned for 15 seconds with pure water

In and operation: at H ₂sO ₄aq (H ₂sO ₄concentration is 0.05mol/L, and temperature is 30 DEG C) in dipping 20 seconds

2nd matting: cleaned for 120 seconds with pure water

Drying process: placed for 60 seconds under the temperature environment of 100 DEG C

2nd example (hereinafter referred to as the 2nd Saponification Conditions) of stronger saponification treatment condition is as follows.

Saponifying process: flooded for 120 seconds in the KOH aqueous solution (KOH concentration is 1.5mol/L, and temperature is 55 DEG C)

1st matting: cleaned for 15 seconds with pure water

In and operation: at H ₂sO ₄aq (H ₂sO ₄concentration is 0.1mol/L, and temperature is 30 DEG C) in dipping 20 seconds

2nd matting: cleaned for 120 seconds with pure water

Drying process: placed for 60 seconds under the temperature environment of 120 DEG C

The saponifying process condition of more weak saponification process is as follows: by concentration be more than 1.0mol/L below 1.4mol/L scope in the KOH aqueous solution be used as alkali aqueous solution, the temperature of this KOH aqueous solution more than 20 DEG C in the scope of less than 40 DEG C, for the dipping time of the film 10 of this KOH aqueous solution more than 30 seconds in the scope of less than 130 seconds.In addition, the 1st matting in more weak saponification process, in identical with the condition in above-mentioned stronger saponification process respectively with each condition of operation, the 2nd matting and drying process.

The example (hereinafter referred to as the 3rd Saponification Conditions) of more weak saponification treatment condition is as follows.

Saponifying process: flooded for 120 seconds in the KOH aqueous solution (KOH concentration is 1.1mol/L, and temperature is 35 DEG C)

1st matting: cleaned for 15 seconds with pure water

2nd matting: cleaned for 120 seconds with pure water

Be adsorbed in by making the compound molecule comprising iodine the film be made up of polyvinyl alcohol (Polyvinyl Alcohol, PVA) and make PVA make polarizing coating 17 with the compound molecule orientation comprising iodine.At the caking agent of the bonding middle use PVA system of film 10 and polarizing coating 17.In addition, polarizing coating 17 is not limited to this, as long as the general film being used as polarizing coating, then can be any film.Further, in the present embodiment, polarizing coating 17 two face adhering films 10 and become Polarizer 20, but be not limited to this structure.Such as, also can only at the one side adhering film 10 of polarizing coating 17, the outmost surface that can also be bonded with film 10 on two of polarizing coating 17 face arranges the protective film of PET etc.

Film 10 by implementing saponification process and swelling, further moisture absorption and become easily swelling.Therefore, implement saponification process after the particulate 14 of (after saponification process) from the height H of the outstanding height H k [unit: nm] of pellicular front 10a lower than (before saponification process) before implementing saponification process.About the film 10 after saponification process, also film 10 before treatment with saponification is identical, when the height H k of projection 15 is more than 30nm, compared with the situation being less than 30nm with the height H k of projection 15, the local of reducing overlapping film 10 attaching each other or to improve the effect of sliding larger.Along with projection 15 uprises, the effect reducing attaching or raising sliding increases, and when the height H k of projection 15 is more than 40nm, the effect of the attaching between the local of the film 10 that minimizing is overlapping or raising sliding increases further.When film 10 carries out saponification process under above-mentioned stronger Saponification Conditions, the effect that the minimizing after saponification process attached and gave sliding is especially high.Further, identical with before saponification process, even if after saponification process, when the height H k of projection 15 is below 100nm, with height H k higher than 100nm situation compared with, the mist degree of film 10 is also lower, therefore preferably.

Further, in the film 10 after saponification process, compared with saponification film 10 before treatment, although height H k is the comparatively small amt of the projection of more than 30nm, there is the effect reducing and attach.At this, by every 1mm of the pellicular front 10a after saponification process ²the height of interior existence is that the number of the projection 15 of more than Hk is set to projection density D k (Hk) [unit: individual/mm ²].Be highly that the projection density D k (30) of more than 30nm is preferably 10 ⁴individual/mm ²above 10 ⁶individual/mm ²in following scope.About the film 10 after saponification process, also film 10 before treatment with saponification is identical, when the projection density D k (30) highly for more than 30nm is 10 ⁴individual/mm ²time above, be less than 10 with projection density D k (30) ⁴individual/mm ²situation compare, reduce the effect that attaches and give the effect of sliding larger.Along with the increase of projection density D k (30), reduce the effect attached and the effect of giving sliding increase, when projection density D k (30) is 2 × 10 ⁴individual/mm ²time above, the effect reducing effect and the imparting sliding attached increases further.Further, when projection density D k (30) is 10 ⁶individual/mm ²time following, be greater than 10 with projection density D k (30) ⁶individual/mm ²situation compare, the mist degree of film 10 is suppressed lower.When projection density D k (30) is 5 × 10 ⁵individual/mm ²time following, the mist degree of film 10 is suppressed lower.In addition, about projection density D k (40), the scope that the effect that minimizing attaches is larger with the effect of giving sliding is also identical with projection density D k (30) with the scope suppressing lower by mist degree.

And, the surperficial 20a of Polarizer 20 is owing to having the structure identical with the pellicular front 10a after saponification process, therefore, about Polarizer 20, under the condition identical with the film 10 after above-mentioned saponification process, also have and reduce Polarizer 20 attaching each other and the effect of imparting sliding.

Below, utilize Fig. 4 to have the situation of the film 10 after two panels saponification film 10 before treatment, saponification process or Polarizer 20 (during general designation, being called film etc. 10,20) to overlap and coil into web-like and the situation becoming film rolling is described.If overlap has two panels film etc. 10,20, then in each film etc. 10,20, pellicular front 10a, 20a of arbitrary film is mutually opposing and contact.On the other hand, in film rolling, batch lap at film etc. 10,20, pellicular front 10a, 20a are not only mutually opposing and contact, but also are applied in contact surface pressure.In film rolling, film etc. 10,20 thinner, put on the contact surface pressure of batching lap higher.Further, the Young's modulus of film etc. 10,20 is lower, puts on the contact surface pressure of batching lap higher.Further, the length of film etc. 10,20 is longer, puts on the contact surface pressure of batching lap higher owing to rolling tightly.

No matter when overlap has two panels saponification film 10 before treatment, or when becoming film rolling, opposed two pellicular front 10a are all formed with the projection 15 formed by particulate 14.By these projections 15, can mutually directly contact by overslaugh opposed two pellicular front 10a in local.Therefore, overlapping film 10 can not attach local mutually.

When saponification film 10 before treatment coils into film web-like, contact surface pressure puts on two opposed pellicular front 10a further.Now, also by projection 15, two pellicular front 10a that locally overslaugh is opposed directly contact mutually, and the lap of film 10 can not attach local mutually.Therefore, even if be subject to the impact of contact surface pressure, also produce between the lap of film 10 and slide.

And, because film 10 is thinning or the Young's modulus of lengthening film 10 or reduction film 10, therefore put on the contact surface pressure of film 10 higher time, also lower with the contact surface pressure putting on film 10 situation is identical, is reduced the mutual attaching of the lap of film 10 by projection 15.That is, the generation of adhesion is reduced.Therefore, the static friction coefficient between the lap of film 10 keeps lower, produces slip between which.Thus, recess can not be produced in film rolling, and wrinkle etc. can not be produced on the film 10 batched.

In the past, the length of film was longer, and such as, in the scope of more than 2000m below 10000m, then in film rolling, lap attaches each other because of contact surface pressure.In contrast, in film 10, even if be this length, also attaching can not be produced in film rolling.Further, film rolling when no matter to be film 10 be Young's modulus is lower, film rolling time still thin, all can reduce attaching.

Even if during film 10 after overlap has two panels saponification process, also identical with the situation of above-mentioned saponification film before treatment 10, two panels film 10 can not attach local mutually.Further, even if also identical when the film 10 after saponification process coils into film web-like, the lap of film 10 can not attach local mutually.And, recess can not be produced in film rolling, and wrinkle etc. can not be produced on the film 10 batched.No matter be the situation that overlap has two panels Polarizer 20, or Polarizer 20 to coil into the situation of film web-like all identical.

By aftermentioned solution film-forming equipment 30 (with reference to figure 5), manufacture film 10 by the 1st dope 41 and the 2nd dope 42.Form the 1st dope 41 of main film body 12 for comprising the 1st dope composition of the liquid state as the cellulose acylate of polymkeric substance, additive and solvent.Cellulose acylate and additive are contained in as solid substance in the 1st dope composition.Cellulose acylate is dissolved in solvent, and additive is not dissolved in solvent and is scattered in solvent.Cellulose acylate in 1st dope 41 and the ratio of additive and each composition of main film body 12 are than identical.

The 2nd dope 42 forming top layer 13 is except comprising the solid substance identical with the 1st dope 41 and solvent, also comprises the 2nd dope composition of the liquid state of the particulate 14 as solid substance.The ratio of cellulose acylate, additive and the particulate 14 in the 2nd dope 42 and each composition on top layer 13 are than identical.Form the 1st dope 41, concentration that the ratio of composition of the 2nd dope 42 considers the solid substance of each dope respectively and form main film body 12, the ratio of composition on top layer 13 decides.

At this, particulate 14 is usual to be scattered in the raw material of state as the 2nd dope 42 of the dispersion liquid in dispersion agent, and for the preparation of the 2nd dope 42.Also the 1st particulate 14 can be used simultaneously to be scattered in the 1st dispersion liquid in the 1st dispersion agent and the 2nd particulate 14 and to be scattered in the 2nd dispersion liquid in the 2nd dispersion agent.At this, the dispersion state of the particulate 14 in the 2nd dope 42 is roughly the same with the dispersion state of the particulate 14 in this dispersion liquid, the dispersion state of the particulate 14 in the 2nd dope 42 is designated as identical with the dispersion state of particulate 14 in dispersion liquid for the preparation of the 2nd dope 42 therefore.

In the 2nd dope 42, particulate 14 is the pattern of offspring and disperses.The particulate 14 that aggregate particle size r2 is more than 0.7 μm is preferably more than 30% relative to the proportional N (0.7) [unit: %] that contains of particulate 14 sum comprised in the 2nd dope 42, is more preferably more than 50% containing proportional N (0.7).The particulate 14 of the aggregate particle size of more than 0.7 μm is comprised by the 2nd dope 42 forming top layer 13, as mentioned above, the height H desired by top layer 13 can be formed with desired projection density D (H), Dk (Hk), the projection 15 of Hk.Therefore, about the film 10 using this 2nd dope 42 to manufacture, film 10 attaching each other during overlapping film 10 is reduced, and gives sliding to its pellicular front 10a.

At this, following definition represents the aggregate particle size r2 of the diameter of the offspring of particulate 14.When the shape of offspring is spherical, its diameter is set to aggregate particle size r2, diameter when being similar to spherical when subglobular by offspring is set to aggregate particle size r2.When the shape of offspring is spheroid, the length of major axis is set to aggregate particle size r2, when close to spheroid, the length of major axis when offspring being similar to spheroid is set to aggregate particle size r2.Obtain the aggregate particle size r2 of the particulate 14 comprised in the 2nd dope 42 as follows.Make the comparatively unfertile land extension of the 2nd dope 42 in the plane, for this plane, such as use scanning electron microscope (Scanning Electron Microscope, SEM) to be amplified to 3000 times and carry out surface observation, then can obtain the surface observation image of each offspring.For the surface observation image of this each offspring, carry out matching with justifying approximate or oval being similar to.During with circle approximate fits, the value of diameter is set to aggregate particle size r2, during with oval approximate fits, the length of major axis is set to aggregate particle size r2.

The mixture of methylene dichloride, methyl alcohol and butanols is for the solvent 53 in the 1st dope 41 and the 2nd dope 42.Further, although employ above-mentioned solvent in the present embodiment, other any solvents be generally used in the solution film-forming manufacturing cellulose acylate film can also be used.Further, when each component of polymer on main film body 12 and top layer 13 not being set to cellulose acylate, determine for the solvent 53 in the 1st dope 41 and the 2nd dope 42 according to used component of polymer.

The solution film-forming manufacturing film 10 such as carries out in the solution film-forming equipment 30 of Fig. 5.Solution film-forming equipment 30 possesses dope preparation facilities 31, casting device 32, tenter machine 35, roller drying installation 36 and take-up mechanism 37 successively from upstream side.

Dope preparation facilities 31 is for making above-mentioned 1st dope 41 and the 2nd dope 42.Dope preparation facilities 31 can be arranged at the outside of solution film-forming equipment 30, instead of in solution film-forming equipment 30.Now, the 1st dope 41 produced and the 2nd dope 42 are temporarily stored in be preserved in container etc.Dope preparation facilities 31 possesses dissolving portion 43, mixing unit 46, through part 47 and filter house 48,49.

If supply cellulose acylate 52 and solvent 53, then these carry out mixing and carry out heating and stirring etc. by dissolving portion 43.Thus, the raw material dope 54 (raw material dope preparation section) that cellulose acylate 52 is dissolved in the liquid state in solvent 53 is made.If a part for raw material dope 54 and additive 59 are mixed supply, then filter house 48 carries out filtration to be made the 1st dope 41 to it.

If supply cellulose acylate 52, solvent 53 and particulate 14, then these carry out mixing and stir the mixture (mixture preparation section) obtaining liquid state by mixing unit 46.Through part 47 is configured at the downstream of mixing unit 46, if supply the mixture of this liquid state from through part 47, then implements ultrasonic wave to this mixture, particulate 14 is disperseed in the mixture, thus obtains particle dispersion liquid 58 (microparticulate operation).In addition, also ball mill can be used replace enforcement ultrasonic wave in through part 47.If another part of the particle dispersion liquid 58 obtained by through part 47, raw material dope 54 and additive 59 are mixed supply, then filter house 49 is carried out mixing (mixed processes), and carries out filtration to be made the 2nd dope 42 (filter progress).

Casting device 32 is for forming film 10 by the 1st dope 41 and the 2nd dope 42.Casting device 32 possesses travelling belt 62, the 1st roller 63 and the 2nd roller 64.Travelling belt 62, for being formed as the circulation curtain coating supporting mass of ring-type, is SUS system.Travelling belt 62 is wound in the side face of the 1st roller 63 and the 2nd roller 64.At least one in 1st roller 63 and the 2nd roller 64 has driving part (not shown), is circumferentially rotated by driving part.By this rotation, transmitted with the travelling belt 62 of circumferential contact, by this transmission, travelling belt 62 carries out circulating and being continuously traveling along long side direction.

The curtain coating mould 65 of spue the 1st dope 41 and the 2nd dope 42 is possessed above travelling belt 62.The 1st dope 41 and the 2nd dope the 42,1st dope 41 and the 2nd dope 42 spue continuously with overlapped state curtain coating on travelling belt 62 by the travelling belt 62 from curtain coating mould 65 to delivery status, thus forms casting films 66.In addition, the 1st dope 41 spues from the discharge opening 65a of curtain coating mould 65 with the form being sandwiched in the 2nd dope 42.

1st roller 63 and the 2nd roller 64 possess the temperature regulator (not shown) controlling all surface temperatures respectively.The temperature of travelling belt 62 is adjusted by each all surface temperatures controlling the 1st roller 63 and the 2nd roller.

About from the 1st dope 41 of curtain coating mould 65 to travelling belt 62 and the 2nd dope 42 i.e. so-called liquid pearl, the upstream on the direct of travel of travelling belt 62 possesses decompression chamber (not shown).This decompression chamber attracts the atmosphere in the upstream side region of the 1st dope 41 and the 2nd dope 42 spued and reduces pressure to described region.

Make casting films 66 be cured to can to tenter machine 35 transmit degree after, peel from travelling belt 62 with the state comprising solvent 53.With regard to stripping, carry out with the solvent containing ratio in the scope of below more than 10 quality % 100 quality % during dry curtain coating mode, carry out with the solvent containing ratio in the scope of below more than 100 quality % 300 quality % during cooling curtain coating mode.Dry curtain coating mode is mode casting films 66 being solidified mainly through drying, and cooling curtain coating mode is mainly through cooling the mode making casting films 66 gelation solidify.In addition, the solvent containing ratio in this specification sheets be the quality of the film 10 being in wetting regime is set to X, when the quality after this film 10 drying is set to Y, by { the value of the so-called dry basis that (X-Y)/Y} × 100 are obtained.

When stripping, with the roller stripped (hereinafter referred to as angle stripper) 70 tread support membrane 10, fixing keep peeling casting films 66 from travelling belt 62 strip position.If travelling belt 62 carries out circulating and from the casting position stripping position and be back to curtain coating the 1st dope 41 and the 2nd dope 42, then the 1st dope 41 that curtain coating is new again and the 2nd dope 42.

Also supply conduit (not shown) can be set in the mode that the curtain coating face of the formation casting films 66 with travelling belt 62 is opposed.This supply conduit Exhaust Gas, promotes the drying of the casting films 66 passed through.

The casting films 66 stripped with angle stripper 70 i.e. film 10 is directed to tenter machine 35.Tenter machine 35 holding member 71 keeps each sidepiece of film 10, promotes the drying of film 10 simultaneously.As the holding member 71 of tenter machine 35, use clip and pin etc.Clip, by clamping film 10, is sold and is run through film 10 by through-thickness and keep film 10 respectively.

Tenter machine 35 keeps film 10 with holding member 71 and transmits along long side direction, gives the tension force on width simultaneously, expands the width of film 10.This tenter machine 35 possesses the conduit 72 dry gas being flowed to carry out near film 10 to supply.Film 10 is transmitted, simultaneously by promoting dry from the dry gas of conduit 72, and by the time changing width of holding member 71 in regulation.

Roller drying installation 36 is for the film 10 of dry delivery status.The delivery direction that roller drying installation 36 possesses along film 10 is arranged with multiple multiple rollers 73, air conditioning machinery (not shown) and chamber (not shown).In multiple roller 73, have the driving roll circumferentially rotated, film 10 is sent to downstream by the rotation of this driving roll.Air conditioning machinery attracts the atmosphere of chamber interior, regulates the humidity and temperature of the gas attracted etc. afterwards this gas to be sent into chamber interior again.Thus, the temperature and humidity etc. of chamber interior remains constant.The film 10 supplied from roller drying installation 36 is coiled into web-like by take-up mechanism 37.In addition, can cooling room (not shown) be set between roller drying installation 36 and take-up mechanism 37.This cooling room was cooled to room temperature before batching the film 10 by inside.

Solution film-forming equipment 30 is an example of embodiments of the present invention, also can be other solution film-forming equipment.Such as, as curtain coating supporting mass, also travelling belt 62 can be replaced for the cylinder (not shown) circumferentially rotated.During cooling curtain coating mode, by more for the situation that cylinder is used as curtain coating supporting mass.Further, also can arrange between tenter machine 35 and roller drying installation 36 and have and the tenter machine of tenter machine 35 same structure (not shown).

The effect of said structure is described.If cellulose acylate 52 and solvent 53 are sent to dissolving portion 43, then carry out mixed merga pass heating and stirring etc. and be made raw material dope 54 (raw material dope preparation section).A part for raw material dope 54, before being directed to filter house 48, adds additive 59, is undertaken filtering and become the 1st dope 41 with the state mixed with additive 59 by filter house 48.

If particulate 14, cellulose acylate 52 and solvent 53 are directed to mixing unit 46, are then mixed by mixing unit 46 and stir, thus obtaining liquid mixture (mixture preparation section).At this, the proportional N (0.7) that contains about the particulate 14 comprised in the 2nd dope 42 is preferably more than 30%.This mixture is sent to through part 47 from mixing unit 46.Particulate 14 in this mixture is scattered in mixture by through part 47, thus obtains particle dispersion liquid 58 (microparticulate operation).In another part of raw material dope 54, add particle dispersion liquid 58, then add additive, and be directed to filter house 49 and carry out mixing (mixed processes), undertaken filtering by filter house 49 and be made the 2nd dope 42 (filter progress).

1st dope 41 and the 2nd dope 42 are directed to curtain coating mould 65 continuously, are spued continuously from discharge opening 65a.With state curtain coating on travelling belt 62 of the order overlap of the 2nd dope 42, the 1st dope 41, the 2nd dope 42, thus form casting films 66.Be formed at casting films 66 on the travelling belt 62 in advancing after possessing self-supporting, stripped from travelling belt 62 with the state comprising solvent 53, thus be made film 10.

Film 10 is sent to tenter machine 35, with the state by holding member 71 Max. Clearance _M., passes through in the atmosphere of the dry gas supplied from conduit 72.Thus, the drying of film 10 is promoted.The film 10 coming from tenter machine 35 is directed to roller drying installation 36, dried during chamber (not shown) inside by this roller drying installation 36.The film 10 of drying is directed to take-up mechanism 37, coils into web-like.

In the 2nd dope 42 particulate 14 relative to cellulose acylate 52 mass ratio Wp [unit: quality %] and about particulate 14 containing proportional N (0.7), with pellicular front 10a on projection density D (30) [unit: individual/mm ²] between there is dependency.Projection density D (30) increases along with mass ratio Wp with containing the increase of proportional N (0.7).At this, mass ratio Wp is the ratio defined by (being added into the total mass of the particulate in dope)/(total mass for the cellulose acylate in dope).In addition, the measuring method by recording in aftermentioned embodiment is obtained respectively containing proportional N (0.7) and projection density D (30).And, about projection density D k (30), projection density D (40), projection density D k (40) etc., also same with projection density D (30), there is the tendency increased along with mass ratio Wp and the increase containing proportional N (0.7).

As an example, if mass ratio Wp is located in the scope of below more than 0.1 quality % 0.3 quality %, the primary particle size r1 of particle is located in the scope of more than 12nm below 20nm, then as shown in Figure 6, known projection density D (30) roughly increases along with the increase containing proportional N (0.7).Expression shown in Figure 6 is containing the straight line U1 of the dependency between proportional N (0.7) and projection density D (30).In addition, if reduce mass ratio Wp, then straight line U1 is to downside (side that raised density D (30) reduces) skew in figure 6, if improve mass ratio Wp, then straight line U1 offsets to upside (side that raised density D (30) increases) in figure 6.Further, be not limited to projection density D (30), about projection density D (40) and projection density D (50), also increase along with mass ratio Wp with containing the increase of proportional N (0.7).

But, when using the 2nd dope 42 containing softening agent, when namely containing softening agent in top layer 13, because implementing saponification process, the pellicular front 10a (with reference to figure 1, Fig. 2) of the film 10 sometimes after saponification process produces sticky feeling (tackiness).When especially carrying out saponification process under more weak Saponification Conditions, there is the tendency producing this sticky feeling.Saponification Conditions is stronger, and softening agent is more easily decomposed, and when for above-mentioned stronger Saponification Conditions, is decomposed and removes from pellicular front 10a in saponification process.But when for above-mentioned more weak Saponification Conditions, the decomposition process of softening agent does not reach the degree removed from pellicular front 10a, the softening agent that the state of therefore thinking to decompose midway remains becomes the reason of sticky feeling.

Therefore, when being supplied to above-mentioned more weak Saponification Conditions, more preferably use the 1st particulate 14 that primary particle size r1 is mutually different and the 2nd particulate 14 simultaneously.Specifically, use the 1st particulate 14 in the scope of more than 16nm below 30nm of primary particle size r1 and primary particle size r1 to be less than the 1st particulate 14 and the 2nd particulate 14 in the scope of more than 5nm below 15nm simultaneously.Thereby, it is possible to the pellicular front 10a manufactured in fig. 2 is formed with the film (not shown) of projection 15a, the 15b with more than 30nm height H and the projection with the height H in more than 10nm below 30nm scope.In addition; now in the 2nd dope 42; preferably the 1st particulate 14 is located in the scope of below more than 0.10 quality % 0.30 quality % relative to the mass ratio Wp1 of cellulose acylate 52, and the 2nd particulate 14 is located in the scope of below more than 0.03 quality % 0.30 quality % relative to the mass ratio Wp2 of cellulose acylate 52.By also forming the projection of the height H had in more than 10nm below 30nm scope, the attaching of the film after the saponification process under more weak Saponification Conditions is reliably inhibited further.Further, even if also form the projection of the height H had in more than 10nm below 30nm scope, because this projection is less, therefore the rising of mist degree also can be inhibited.The primary particle size r1 of the 1st particulate 14 is preferably in the scope of more than 16nm below 30nm, preferred in the scope of more than 16nm below 20nm further.The primary particle size r1 of the 2nd particulate 14 is preferably in the scope of more than 5nm below 15nm, preferred in the scope of more than 7nm below 12nm further.Not only in the 2nd dope 42, and in the 1st dope 41, also can use the 1st particulate 14 and the 2nd particulate 14 that primary particle size r1 is mutually different simultaneously.

In the present embodiment, manufacture the film 10 of three layers of this multilayered structure, but as mentioned above, the film of the present invention to single layer structure also has effect.Further, in the present embodiment, manufacture the film 10 of the three-decker be made up of main film body 12 and a pair top layer 13, but be not limited to this by the film that the present invention obtains.Such as, also more than four layers can be set to by multilayer curtain coating and coating etc.In addition, when manufacturing the film of single layer structure too, more than 30% is preferably about particulate 14 containing proportional N (0.7).Further, the projection density D (30) of the pellicular front 10a of manufactured film is 10 ⁴individual/mm ²above 10 ⁶individual/mm ²in following scope, the projection density D k (30) carrying out the pellicular front 10a after saponification process also in the same manner as before saponification process 10 ⁴individual/mm ²above 10 ⁶individual/mm ²in following scope.

Below, 4 embodiments relevant with the present invention are enumerated.

[embodiment 1]

As embodiment 1, carry out 17 kinds of experiment 1-A ~ 1-Q.In this embodiment 1, commodity in use name is respectively the dispersion liquid of 3 kinds of particulates 14 of R972, NX90S, RX200 (being Nippon Aerosil Co., Ltd. to manufacture).At this, about the dispersion liquid of these 3 kinds of particulates 14, be summarised in following table 1.In the dispersion liquid of each trade(brand)name described in each hurdle of " dispersion liquid " of table 1, the material of particulate 14 is formed respectively shown in " particulate " hurdle, the material of dispersion agent is formed shown in " dispersion agent " hurdle, the concentration [unit: quality %] of the particulate 14 in dispersion agent shown in " particulate loading " hurdle, the mean value [unit: nm] of the primary particle size r1 of particulate 14 shown in " primary particle size " hurdle, the mean value [unit: μm] of the aggregate particle size r2 of particulate 14 shown in " aggregate particle size mean value " hurdle, about particulate 14 shown in " containing proportional N (0.7) " hurdle containing proportional N (0.7) [unit: %].In addition, " particulate " is identical in 3 kinds of dispersion liquids with " dispersion agent ", is therefore combined respectively on the hurdle in table 1.CH in " dispersion agent " hurdle ₂cl ₂: CH ₃the ratio of OH is ratio in mass.

[table 1]

At this, the aggregate particle size r2 of particulate 14 is the aggregate particle size based on the definition described in above-mentioned embodiment, as mentioned above, uses SEM to be amplified to 3000 times and carries out surface observation, obtain aggregate particle size thus for each particulate 14.Obtain the size distribution of particulate 14 according to the result of the aggregate particle size r2 obtained for each particulate 14, obtain median according to this size distribution, this median is set to the mean value of aggregate particle size r2.Further, according to the size-grade distribution of particulate 14 obtain about particulate 14 containing proportional N (0.7).In addition, this obtain about particulate 14 containing proportional N (0.7) for after being added into dope containing proportional N (0.7).

The trade(brand)name of the dispersion liquid of the particulate 14 used in each experiment is shown in " dispersion liquid " hurdle of " particulate " in the hurdle of each example of table 2.Further, particulate 14 is shown in " mass ratio " hurdle of " particulate " in each experiment of table 2 relative to the mass ratio Wp of cellulose acylate 52.In addition, experiment 1-L is relative to comparative experiments of the present invention, does not add dispersion liquid for this experiment 1-L, is expressed as "-" in " dispersion liquid " hurdle of therefore table 2.

Further, the solid substance beyond the particulate 14 comprised in the dope for each experiment is set to any one in following solid substance A ~ C.In arbitrary experiment, in the dope of all three layers, all use the solid substance of identical type.Solid substance beyond the particulate 14 used in each experiment is shown in " solid substance kind " hurdle in each experiment of table 2.In addition, at this, the ratio of entirety during with the ratio of mass parts unit representation for the solid substance beyond the solid substance being derived from raw material dope 54 in above-mentioned embodiment and the particulate 14 being derived from particle dispersion liquid 58 is added together.

Solid substance A is made up of composition shown below.The length direction of film 10 using solid substance A to manufacture and the average elastic modulus of width are 4.5GPa.

(solid substance A)

Cellulosetri-acetate (TAC) 100.0 mass parts

Sucrose benzoate 7.5 mass parts

Sucrose acetoisobutyrate 2.5 mass parts

UV light absorber TINUVIN (registered trademark) 928 (BASF Japan Ltd. manufactures) 2.0 mass parts

At this, the viscosity that above-mentioned cellulosetri-acetate is degree of substitution with acetyl group is 2.86, viscosity average polymerization degree is 306, water ratio is 6 quality % in 0.2 quality %, dichloromethane solution is the powder of 310mPas.Sucrose benzoate and Sucrose acetoisobutyrate are softening agent.Further, TINUVIN (registered trademark) 928 with 2-(2H-benzotriazole-2-base)-6-(1-methyl isophthalic acid-styroyl)-4-(1,1,3,3-tetramethyl butyl) phenol for principal constituent.

Solid substance B is made up of composition shown below.The length direction of film 10 using solid substance B to manufacture and the average elastic modulus of width are 3.0GPa.

(solid substance B)

Cellulosetri-acetate (TAC) 100.0 mass parts

Polyester plasticizer 25.0 mass parts

Solid substance C is made up of composition shown below.The length direction of film 10 using solid substance C to manufacture and the average elastic modulus of width are 3.0GPa.

(solid substance C)

Acrylate copolymer 100.0 mass parts

Further, solvent shown below is used in the solvent comprised in the dope of each experiment.

(solvent)

Methylene dichloride 330.0 mass parts

Methyl alcohol 64.0 mass parts

Butanols 3.0 mass parts

In arbitrary experiment, dope all uses the dope preparation facilities 31 shown in above-mentioned Fig. 5 to manufacture.At this, for the aftermentioned dope being added with particulate 14, utilize the method identical with the 2nd dope 42 to manufacture, for the dope not adding particulate 14, utilize the method identical with the 1st dope 41 to manufacture.Further, in arbitrary experiment, the concentration of the solid substance forming the dope of main film body 12 is set to 22%, the solid concentration of the dope forming top layer 13 is set to 19%.Further, in arbitrary experiment, casting films 66 is formed by the casting device 32 identical with the casting device shown in above-mentioned Fig. 5.The dope forming main film body 12 is sandwiched in the dope forming top layer 13, thus forms casting films 66 with the state of three plies.And, strip this casting films 66 to form film 10.Afterwards, in the solution film-forming equipment 30 of Fig. 5, carry out the process identical with above-mentioned embodiment by each device being arranged at the downstream of casting device 32.

At this, about experiment 1-A ~ 1-E, 1-J ~ 1-Q, in the dope of all three layers, all add particulate 14.On the other hand, about experiment 1-F ~ 1-I, only in the dope forming top layer 13, particulate 14 is added.The layer adding fine-grained dope in each experiment is shown in " adding layers " hurdle of " particulate " in each experiment of table 2.At this, for the example being added with particulate 14 in the dope of all three layers, be expressed as " holostrome ", for the example being only added with particulate 14 in the dope forming top layer 13, be expressed as on " top layer ".

[table 2]

For manufactured each film 10, obtain overall consistency (total projection density D [unit: individual/mm of the projection 15 on pellicular front 10a by the following method ²]) and the height carried out respectively before and after saponification be density (projection density D (the 30) [unit: individual/mm of the projection 15 of more than 30nm ²], Dk (30) [unit: individual/mm ²]).Saponification process is set to stronger saponification process, and its condition is above-mentioned 1st Saponification Conditions.

Observe from the direction substantially vertical with the pellicular front 10a of manufactured each film 10 (before the saponification process the 1st Saponification Conditions), obtain the image of this observation.This observation uses scanning type probe microscope (SPA400, SII Nano Technology Inc. manufactures), under AFM (Atomic Force Microscope, atomic force microscope) pattern, carry out the scope of 100 μm × 100 μm.Below, the observation image obtained at this is called afm image.In afm image, according to height outstanding from the surface of pellicular front 10a on the position observed, demonstrate the brightness of the pixel corresponding with this position higher.As an example of afm image, the afm image relevant with the film 10 manufactured in experiment 1-D is shown in Fig. 7.

If according to the character of the afm image that brightness uprises along with projecting height, in afm image by the brightness settings of regulation be threshold value to carry out binary conversion treatment, then the position more than height that can specify from the surperficial separation and Extraction of pellicular front 10a.Utilize this character, for each afm image, the part of carrying out the surface from pellicular front 10a to give prominence to more than 10nm is set to lightness and binary conversion treatment part being in addition set to dark brightness and being separated.At this, be illustrated in Fig. 8 by carrying out one of the image of this binary conversion treatment to the afm image obtained in experiment 1-D.

Using highly for brightness during 10nm is as in the image after threshold value carries out binary conversion treatment, each several part (island of each grey such as, in Fig. 8) becoming lightness is identified as respectively height for the projection of more than 10nm and detecting.By counting the quantity obtaining the projection being highly more than 10nm to the quantity of the part becoming this lightness.And, the quantity of this projection is multiplied by 100 and is scaled every 1mm ²the number of quantity of projection as the total projection density Ds 1 of local in the region of this afm image of acquisition.In each experiment, obtain multiple afm image, and obtain total projection density D 1 of multiple local, these arithmetical mean is set to the total projection density D in each experiment.This total projection density D is shown in " the total projection density D " hurdle in each experiment of table 3.In addition, shown in " total projection density D " hurdle, significant figure are the value of two.

By above-mentioned total projection density D ask in method threshold value when carrying out binary conversion treatment to change to give prominence to from the surface of pellicular front 10a more than 30nm time brightness, other then utilize the method identical with the method obtaining total projection density D to obtain the projection density D (30) in each experiment.At this, the afm image for obtaining in experiment 1-D shown in Figure 9, carries out an example of the image of binary conversion treatment as threshold value using brightness when being highly 30nm.This projection density D (30) is shown in " projection density D (the 30) " hurdle in each experiment of table 3.In addition, shown in " projection density D (30) " hurdle, significant figure are the value of 3.

After saponification process being carried out to manufactured each film 10 under the 1st Saponification Conditions, about the acquisition process of afm image, binary conversion treatment and obtain projection quantity before process, utilize method same as described above to obtain projection density D k (30) in each experiment.This projection density D k (30) is shown in " projection density D k (the 30) " hurdle in each experiment of table 3.In addition, shown in " projection density D k (30) " hurdle, significant figure are the value of 3.

For each film 10 before and after the saponification process under the 1st Saponification Conditions in each experiment, the following degree evaluated attaching and reduced.First, each film 10 is cut into the foursquare film of 7cm × 7cm by overlap 3.Then, with the state of overlapping 3 each films 10, carry out damping in 24 hours under the condition of temperature 25 DEG C, humidity 50% after, under being placed in the environment of temperature 40 DEG C, humidity 20% with the state of overlapping 3.And, on 3 overlapping each films 10, load the counterweight of 5kg and after placing 24 hours, obtain the ratio S [unit: %] of area of attachment relative to the contact area of film 10 of film 10.With 4 stages of following A ~ D, the ratio S of calculated area of attachment is evaluated.This evaluation result is shown in " attach and the evaluate " hurdle in each experiment of table 3.Saponification evaluation before treatment shown in " before saponification process " hurdle respectively, the evaluation after saponification process shown in " after saponification process " hurdle.If this attaching is evaluated among A, B, C, then it is the film 10 in the scope that practicality is allowed.

A: be less than 20%

More than B:20% and be less than 30%

More than C:30% and be less than 40%

More than D:40%

For each film 10 before treatment of the saponification in each experiment, use haze meter (NDH-5000, Nippon Denshoku Industries Co.Ltd.), measure mist degree according to JIS-K-7105.The measurement result of mist degree is shown in " mist degree " hurdle in each experiment of table 3.

[table 3]

By table 2 and table 3 known below.Observe following tendency: although create some deviations, projection density D (30) roughly increases along with the increase containing proportional N (0.7) and mass ratio Wp of dispersion liquid.And it is known: compared with when being holostrome with the layer being added with particulate 14, when described layer is top layer, the mist degree of manufactured film to be suppressed lower.

Further, total projection density D and before treatment the attaching between the result evaluated of saponification do not observe dependency.Such as, in experiment 1-C, 1-F, 1-N, 1-P, 1-Q, total projection density D is 90000/mm ², but saponification attaching evaluation before treatment is respectively A, A, B, C, C, creates larger difference.On the other hand, projection density D (30) and before treatment the attaching between the result evaluated of saponification observed dependency.Be 20000/mm at projection density D (30) ²in above experiment 1-A ~ 1-K, saponification attaching evaluation before treatment is A.At projection density D (30) at 16000/mm ²above and be less than 20000/mm ²scope in experiment 1-O in, saponification attaching before treatment is evaluated as B.Be 10000/mm at projection density D (30) ²above and be less than 16000/mm ²scope in experiment 1-M, 1-N, 1-P, 1-Q in, saponification attaching evaluation before treatment is respectively C, B, C, C.Further, 10000/mm is less than at projection density D (30) ²experiment 1-L in, saponification attaching before treatment is evaluated as D.

Further, observed dependency between the result of the attaching evaluation after projection density D k (30) and saponification process.Be 20000/mm at projection density D k (30) ²in above experiment 1-D, 1-E, 1-G ~ 1-K, the attaching evaluation after saponification process is A.At projection density D k (30) at 10000/mm ²above and be less than 20000/mm ²scope in experiment 1-B, 1-C, 1-F in, the attaching after saponification process is evaluated as B.At projection density D k (30) for being less than 10000/mm ²experiment 1-A, 1-L ~ 1-Q in, the attaching after saponification process is evaluated as D.

And, in experiment 1-N, 1-P, 1-Q of being set to the same terms except solid substance, in experiment 1-P, 1-Q of using solid substance B and C that thin flexible film modulus is lower, saponification attaching before treatment is evaluated as C, is to evaluate the lower evaluation of B than the attaching of the experiment 1-N using solid substance A.On the other hand, improving in experiment 1-G, 1-J, 1-K of projection density D (30) by keeping the same terms beyond solid substance equally, in experiment 1-J, 1-K of using solid substance B and C, attaching is evaluated as A, for evaluating the identical result of A with the attaching of the experiment 1-G using solid substance A.It can thus be appreciated that: compared with using the film of solid substance A, the effect that the minimizing using the film of lower solid substance B and C of Young's modulus to obtain by improving projection density D (30) attaches is larger.

And, for each film 10 that the thickness manufactured in embodiment 1-D, 1-J, 1-K is respectively 20 μm, 40 μm, confirm whether produce recess, wrinkle and adhesion (batching property) because coiling into web-like before and after the saponification process respectively under the 1st Saponification Conditions, result does not all produce recess, wrinkle and adhesion (batching property is good).Further, wherein, confirm to coil into the batching property of web-like after carrying out transparent coating to the thickness each film 10 that is 40 μm, batching property of result is all good.

At this, transparent coating refers to carries out coating to arrange transparent hard-coating layer on the surface of above-mentioned film.As transparent hard-coating layer, preferably use actinic rays curable resin or heat reactive resin.Actinic rays curable resin refers to the layer that the resin solidified there is crosslinking reaction by photoactinic irradiation such as ultraviolet and electron rays is principal constituent.As actinic rays curable resin, there are uv curing resin and electron(beam)curing resin etc., also can for the resin solidified by the photoactinic irradiation beyond ultraviolet and electron rays etc.As uv curing resin, such as, can enumerate ultraviolet hardening acroleic acid polyurethane system resin, ultraviolet hardening polyester acrylate system resin, ultraviolet hardening epoxy acrylate system resin etc.

[embodiment 2]

In embodiments of the invention 2, use above-mentioned solid substance A, the primary particle size r1 of particulate 14 and its addition are set to variable to manufacture 7 kinds of films 10, and confirm to attach effective rising height H to minimizing.In the method that in 7 kinds of films, Stochastic choice is evaluated in above-mentioned attaching, the ratio S of area of attachment is the film of 0% ~ 50%.

For these 7 kinds of films 10, obtaining respectively is highly density (projection density D (the 10) [unit: individual/mm of the projection of more than 10nm ²]), be highly density (projection density D (the 20) [unit: individual/mm of projection of more than 20nm ²]), be highly density (projection density D (the 30) [unit: individual/mm of projection of more than 30nm ²]), be highly density (projection density D (the 40) [unit: individual/mm of projection of more than 40nm ²]), be highly density (projection density D (the 50) [unit: individual/mm of projection of more than 50nm ²]).The density of these projections is all by obtaining as follows: be that threshold value carries out binary conversion treatment to afm image described above by the brightness settings corresponding with the height of each projection, counts and by every 1mm to the block number of lightness ²convert.

About these 7 kinds of films 10, get projection density D (10) at transverse axis, the longitudinal axis gets in the graphic representation of the ratio S of area of attachment and mark and draw, result obtains the graphic representation shown in Figure 10.Transverse axis is got projection density D (30) and is carried out same plotting, and result obtains the graphic representation shown in Figure 11.Transverse axis is got projection density D (40) and is carried out same plotting, and result obtains the graphic representation shown in Figure 12.Further, transverse axis is got projection density D (50) and is carried out same plotting, and result obtains the graphic representation shown in Figure 13.

Graphic representation from Figure 10: projection density D (10) is not for almost to have influential factor to the ratio S of area of attachment.On the other hand, from Figure 11,12, the graphic representation of 13: projection density D (30), projection density D (40) and projection density D (50) are the factor ratio S of area of attachment to stronger dependency.Known projection density D (30), projection density D (40) and projection density D (50) are larger, and the ratio S of area of attachment is less.

Except Figure 10 ~ 13, about these 7 kinds of films 10, also produce and get projection density D (20) at transverse axis, the longitudinal axis gets in the graphic representation of the ratio S of area of attachment the figure (province's sketch map) carrying out marking and drawing.Contribution rate (the multiple coefficient of determination) R is obtained for these 5 graphic representations ².About obtaining this contribution rate R ²result, get at transverse axis the rising height H [unit: nm], the longitudinal axis that become threshold value in above-mentioned 5 graphic representations and get contribution rate R ²graphic representation in mark and draw, result obtains the graphic representation shown in Figure 14.From this graphic representation: highly for the projection of more than 30nm contributes to the ratio S reducing area of attachment, wherein, highly for the projection of more than 40nm contributes to the ratio S reducing area of attachment more, wherein, highly for the projection of more than 50nm contributes to the ratio S reducing area of attachment further.

[embodiment 3]

In the present embodiment 3, use 10 kinds of films 10 by making with above-described embodiment 1,2 identical methods, which kind of particulate is reduce attaching projection with confirming the validity comprise.10 kinds of thin film accidentals select the ratio S of area of attachment in the method evaluated in above-mentioned attaching to be the film of 0% ~ 50%.

From the direction that the pellicular front 10a with these 10 kinds of films 10 is substantially vertical, with SEM (Scanning Electron Microscope, scanning electron microscope) observe, investigate the distribution of the aggregate particle size r2 of the particulate that the pellicular front 10a of each film 10 exists.About these 10 kinds of films 10, get getting in the graphic representation of the ratio S of area of attachment mark and draw containing proportional N (0.7) [unit: %], the longitudinal axis about particulate 14 at transverse axis, result obtains the graphic representation shown in Figure 15.As shown in Figure 15: if become more than 30% containing proportional N (0.7), then the ratio S of area of attachment is less than 20%, if become more than 50% containing proportional N (0.7), then the ratio of area of attachment is less than 10%.Can confirming thus: in order to reduce the attaching between overlapping film, importantly the proportional N (0.7) that contains in film forming dope being set to higher.

[embodiment 4]

Use the dispersion liquid of two kinds of particulates 14 simultaneously and made 3 kinds of films 10 of 3-tier architecture by the method identical with embodiment 1 respectively, for each film 10 obtained in experiment 1-D, 1-E, 1-O of these 3 kinds of films 10 and embodiment 1, following evaluation is reduced the effect attached and is also obtained mist degree.Experiment about the film 10 using two kinds of dispersion liquids to make simultaneously is set to experiment 4-R, 4-S, 4-T, the experiment about each film 10 obtained in experiment 1-D, 1-E, 1-O of embodiment 1 is set to experiment 4-D, 4-E, 4-O.

The dispersion liquid simultaneously used is above-mentioned NX90S and RX200, in table 4, NX90S is designated as the 1st composition, RX200 is designated as the 2nd composition.Be pre-mixed NX90S and RX200, the mixed dispersion liquid be obtained by mixing be used as each raw material of the 1st dope 41 and the 2nd dope 42 by this.In " mass ratio " hurdle of " particulate " in table 4, by each dispersion liquid, the mass ratio Wp of particulate 14 relative to cellulose acylate 52 is shown.In table 4, being designated as "-" in " dispersion liquid " hurdle of " the 1st composition " when not using NX90S, being designated as "-" in " dispersion liquid " hurdle of " the 2nd composition " when not using RX200.About the layer adding fine-grained dope in each experiment, " adding layers " and " solid substance kind " of " particulate " of table 4 is set to and " adding layers " hurdle in table 2, " solid substance kind " method for expressing that hurdle is identical respectively.

In this embodiment 4, carry out the above-mentioned stronger saponification process based on the 2nd Saponification Conditions and the above-mentioned more weak saponification process based on the 3rd Saponification Conditions for each film 10, and reduce the effect of attaching for the film 10 after each saponification process evaluation and obtain mist degree.That reduces the evaluation method of effect and metewand that attach and mist degree asks method in the same manner as in Example 1.Result is shown in table 4.

[table 4]

Claims

1. a film, it possesses following:

Pellicular front, by polymer formation; And

Projection, to be formed on described pellicular front and to be highly more than 30nm, and described projection comprises particulate, and on described pellicular front every 1mm ²in area, with 10 ⁴individual above 10 ⁶individual following scope is formed with described projection.

2. film according to claim 1, wherein,

Described polymkeric substance is cellulose acylate.

3. film according to claim 2, wherein,

Every 1mm on described pellicular front ²in area, with 10 ⁴individual above 10 ⁶individual following scope be formed described pellicular front saponification process after described projection.

4. the film according to Claims 2 or 3, wherein,

The described pellicular front be adhered to by polarizing coating after saponification process uses.

5. film according to any one of claim 1 to 3, wherein,

Described particulate is silicon-dioxide.

6. film according to claim 4, wherein,

Described particulate is silicon-dioxide.

7. a dope composition, it possesses following:

Polymkeric substance;

Solvent, dissolves described polymkeric substance; And

Particulate, disperses with the state of offspring, and aggregate particle size is that the described particulate of more than 0.7 μm is at least 30% relative to described particulate sum containing proportional.

8. dope composition according to claim 7, wherein,

Described polymkeric substance is cellulose acylate.

9. a manufacture method for dope composition, it possesses following steps:

(A) polymkeric substance and solvent are mixed, and at least one by heating and in stirring, described polymer dissolution is made raw material dope in described solvent;

(B) liquid mixture is obtained by carrying out mixing with described polymkeric substance and the congruent polymkeric substance of described solvent phase and solvent and particulate and stir;

(C) in described mixture, described particulate is disperseed as offspring, thus obtains particle dispersion liquid, in described particle dispersion liquid, the described particulate of the aggregate particle size of more than 0.7 μm is at least 30% relative to described particulate sum containing proportional; And

(D) described raw material dope and described particle dispersion liquid are carried out mixing to obtain dope composition.

10. the manufacture method of dope composition according to claim 9, wherein,

In the step C, by applying ultrasonic wave to described mixture, described particulate is disperseed in described mixture as offspring.

The manufacture method of 11. dope compositions according to claim 9, wherein,

In the step C, by using ball mill to make described particulate disperse as offspring in described mixture.

The manufacture method of 12. dope compositions according to any one of claim 9 to 11, wherein,

Described polymkeric substance is cellulose acylate.

13. 1 kinds of solution film-forming methods, it possesses following steps:

(C) described particulate is disperseed in described mixture as offspring, thus obtain particle dispersion liquid, in described particle dispersion liquid, the described particulate of the aggregate particle size of more than 0.7 μm is at least 30% relative to described particulate sum containing proportional;

(D) described raw material dope and described particle dispersion liquid are carried out mixing to obtain dope composition;

(E) casting films is formed by the described dope composition that spues continuously on the supporting mass be continuously traveling from curtain coating mould at described supporting mass; And

(F) film is obtained by peeling described casting films from described supporting mass and carrying out drying.